WO2018147979A1

WO2018147979A1 - A process for preparing silicone polyethers

Info

Publication number: WO2018147979A1
Application number: PCT/US2018/013958
Authority: WO
Inventors: Alix SCHMIDT
Original assignee: Dow Silicones Corp
Current assignee: Dow Silicones Corp
Priority date: 2017-02-09
Filing date: 2018-01-17
Publication date: 2018-08-16
Anticipated expiration: 2019-08-09

Abstract

A process is disclosed for the preparing of silicone polyether by reacting a mixture comprising (A) a polyether having at least one terminally unsaturated hydrocarbon group and an alkali metal content of less than 10 ppm, and an alkaline earth metal content of less than 0.4 ppm, (B) an organohydrogensiloxane having an acid number of less than 0.005, and (C) a hydrosilylation reaction catalyst.

Description

A PROCESS FOR PREPARING SILICONE POLYETHERS

CROSS-REFERENCE TO RELATED APPLICATIONS'

NONE

[0001] This invention relates to a process for the preparation of silicone polyethers. The process is useful to prepare silicone polyethers of improved quality, and is particularly useful when employed in batch or continuous process to achieve residual silicon-hydride content specifications.

[0002] Silicone polyethers (SPEs) are used extensively in a variety of surfactant applications, such as in the production of polyurethane foams, and as ingredients in personal care products. SPEs are typically based on copolymer structures of

polyorganosiloxanes having pendant polyoxyalkylene groups. Most commonly, the copolymer structures of silicone polyethers are the "rake" type, where a predominately linear polyorganosiloxane provides the "backbone" of the copolymer architecture with pendant polyoxyalkylene groups forming the "rake". "ABA" structures are also common, where a pendant polyoxyalkylene group is at each molecular terminal of a linear polyorganosiloxane. (AB)_n silicone polyether block copolymers are also known.

[0003] Commercially, silicone polyethers are typically made via a platinum catalyzed hydrosilylation reaction in large batch reactors or occasionally in continuous processes. Typically a large molar excess of the unsaturated polyether is needed in such hydrosilylation reactions to account for isomerization of terminal vinyl functionality of the polyoxyalkylene to an unreactive internal position. Since it is impossible to separate the silicone polyether product from un-reacted unsaturated polyether starting materials, product quality and performance is limited in certain applications. Even with an excess of unsaturated hydrocarbon reagent, it is often difficult to achieve the near-complete conversion of silicon- hydride functionality that is typically required as a quality specification. As a result, additional polyoxyalkylene reagent or platinum catalyst are added to promote further conversion, adding cost and further decreasing product quality. Thus, a method for preparing silicone polyethers which readily achieves ppm-level silicon-hydride specifications is very useful for improving product quality.

[0004] Previous efforts to improve SPE quality involved the use of unsaturated polyether raw materials which have an alkali metal content of less than 50 ppm, as described in US 8,008,407, which is herein incorporated by reference for its teaching of preparation of silicone polyethers. The advantage described in US 8,008,407 was an ability to achieve a faster hydrosilylation reaction rate when there were lower concentrations of alkali metals (such as Na and K) in the reaction mixture, which is particularly useful for preparing silicone polyethers in a continuous process. The present invention goes one step further by identifying conditions which enable a more complete hydrosilylation reaction regardless of reaction rate, namely through the use of unsaturated polyethers with low alkaline earth metal content. Comparison of reaction rates and reaction completion across a wide variety of hydrosilylation reactions involving unsaturated polyethers of varying alkali metal and alkaline earth metal concentrations shows that the two impurities behave fundamentally differently, with alkaline earth metal (such as Mg and Ca) concentration being significantly linearly correlated to reaction completion while alkali metal concentration is not. Thus, the present invention enables the production of higher quality polyethers in either batch or continuous processes.

BRIEF SUMMARY OF THE INVENTION

[0005] This invention relates to a process for preparing a silicone polyether comprising reacting a mixture comprising:

(A) a polyether having at least one terminally unsaturated aliphatic hydrocarbon group, an alkali metal content of less than 10 ppm, and an alkaline earth metal content of less than 0.4 ppm; and

(B) an organohydrogensiloxane having an acid number of less than 0.005;

(C) a hydrosilylation reaction catalyst.

[0006] The process of the present is particularly useful to prepare silicone polyethers of improved quality via either a batch or continuous process.

DETAILED DESCRPTION OF THE INVENTION

[0007] Component (A) of the present invention is a polyether having at least one terminally unsaturated aliphatic hydrocarbon group, an alkali metal content of less than 10 ppm and an alkaline earth metal content of less than 0.4 ppm. As used herein, "polyether" denotes a polyoxyalkylene copolymer represented by the formula -(C_nH2_nO)- wherein n is from 2 to 4 inclusive. The polyoxyalkylene copolymer unit typically may comprise oxyethylene units - (C2H4O)-, oxypropylene units -(ΟβΗβΟ)-, oxybutylene units -(C4H8O)-, or mixtures thereof.

The oxyalkylene units can be arranged in any fashion to form either a block or randomized copolymer structure, but typically form a randomized copolymer group. Typically, the polyoxyalkylene comprises both oxyethylene units (C2H4O) and oxypropylene units

(Ο_βΗ_βΟ) in a randomized copolymer.

[0008] The polyether (A) may be selected from those having the average formula

R 0(C_nH2_nO)_mR² Formula 1 where n is from 2 to 4 inclusive, m is greater than 2, R¹ is a monovalent terminally unsaturated aliphatic hydrocarbon group containing 2 to 12 carbon atoms, R² is R¹ , hydrogen, an acetyl group, or a monovalent hydrocarbon group containing 1 to 8 carbons.

[0009] In Formula 1 , the polyether is terminated at one end with an unsaturated aliphatic hydrocarbon group containing 2 to 12 carbon atoms, such as an alkenyl or alkynyl group. Representative, non-limiting examples of the alkenyl groups are shown by the following structures; H₂C=CH-, H₂C=CHCH₂-, H2C=C(CH₃)CH₂-, H₂C=CC(CH₃)₂-, H^CHCH^H^, H^^CH^H^H^, and H^CHCH^H^H^H^.

Representative, non-limiting examples of alkynyl groups are shown by the following structures; HC≡C-, HC≡CCH₂-, HC≡CC(CH₃)-, HCsCCiCHs)^, HC≡CC(CH₃)CH₂-. The polyether may also contain an unsaturated aliphatic hydrocarbon group at each terminal end, when R² = R¹ , which will result in the formation of an (AB)_n type of silicone polyether if the organohydrogensiloxane contains at least two SiH units, and in particular terminal SiH units.

[0010] Polyethers having an unsaturated aliphatic hydrocarbon group at a molecular terminal are known in the art, and many are commercially available. Representative, non- limiting examples of polyethers, having an alkenyl end group, useful as component (A) include:

H₂C=CHCH₂0(C₂H₄0)_aH

H₂C=CHCH₂0(C₂H₄0)_aCH₃

H₂C=CHCH₂0(C₂H₄0)_aC(0)CH₃

H₂C=CHCH₂0(C₂H₄0)_a(C₃H₆0)_bH

H₂C=CHCH₂0(C₂H₄0)_a(C₃H₆0)_bCH₃

H₂C=C(CH₃)CH₂0(C₂H₄0)_aH

H₂C=CC(CH₃)₂0(C₂H₄0)_aH

H₂C=C(CH₃)CH₂0(C₂H₄0)_aCH₃

H₂C=C(CH₃)CH₂0(C₂H₄0)_aC(0)CH₃

H₂C=C(CH₃)CH₂0(C₂H₄0)_a(C₃H₆0)_bH

H₂C=C(CH₃)CH₂0(C₂H₄0)_a(C₃H₆0)_bCH₃

HC≡CCH₂0(C₂H₄0)_aH

HC≡CCH₂0(C₂H₄0)_aCH₃

HC≡CCH₂0(C₂H₄0)_aC(0)CH₃

HC≡CCH₂0(C₂H₄0)_a(C₃H₆0)_bH

HC≡CCH₂0(C₂H₄0)_a(C₃H₆0)_bCH₃ where a and b are greater than 0, alternatively a and b independently may range from 0 to 40, with the proviso that a + b > 2.

[0011 ] The polyether may also be selected from those as described in US 6,987,157, which is herein incorporated by reference for its teaching of polyethers.

[0012] The polyether (A) must have an alkali metal content of less than 10 ppm, alternatively, less than 5 ppm, or alternatively less than 2 ppm. As used herein, "ppm" denotes parts per million on a weight basis as determined by ICP-MS method.

[0013] The polyether (A) must have an alkaline earth metal content of less than 0.4 ppm, alternatively, less than 100 ppb. As used herein, "ppb" denotes parts per billion on a weight basis as determined by ICP-MS method.

[0014] Polyethers, such as those useful as component (A), are typically prepared by the base catalyzed polymerization of alkylene oxides, such as ethylene, propylene, or butylene oxide. Generally, the base catalyst is an alkali metal hydroxide such as sodium or potassium hydroxide. The alkali metal often remains in the resulting polyether product. However, techniques are known in the art for removing residual alkali metals for such products. Alternatively, non-alkali metal based catalysts are also known in the art. Thus, polyether (A) may be any polyether having an alkali metal concentration of less than 10 ppm (parts per million) by weight. Such levels of alkali metal may be achieved by removing alkali metals from polyethers having alkali metal concentrations in excess of 10 ppm by any method known in the art. Alternatively, the polyether (A) may be prepared by a process that does not add, or minimizes, the amount of alkali metals such that the resulting concentration of alkali metal is less than 50 ppm. The alkali metal content may be determined by any analytical method or technique known in the art, such as ICP-MS. Some of the methods for removal of alkali metals from polyethers that are known in the art may also introduce alkaline earth metals into the polyether. Alternatively, alkaline earth metals may arrive in the polyether by other means. Polyether (A) may be any polyether having an alkaline earth metal concentration of less than 10 ppm (parts per million) by weight. Alternatively, the polyether (A) may be prepared by a process that does not add, or minimizes, the amount of alkaline earth metals such that the resulting concentration of alkaline earth metal is less than 10 ppm. The alkali metal content may be determined by any analytical method or technique known in the art, such as ICP-MS.

[0015] Component (B) of the present invention is an organohydrogensiloxane. As used herein, an organohydrogensiloxane is any organopolysiloxane containing at least one silicon-bonded hydrogen atom (SiH) per molecule. Organohydrogensiloxanes are well known in the art and are often designated as comprising any number of combination of (R3S1O-1/2), (R2S1O), (RS1O32), (S1O2) siloxy units, where R is independently an organic group or hydrocarbon group. When R is methyl in (R3S1O1/2), (R2SKD), (RS1O3/2), siloxy units of an organopolysiloxane, the siloxy units are often designated as M, D, and T units respectively while the (S1O2) siloxy unit is designated as a Q unit. Organohydrogensiloxanes have similar structures, but have at least one SiH present on a siloxane unit. Thus, methyl based siloxy units in an organohydrogensiloxane can be represented as comprising

M^H siloxy units (Me2HSiOi/2)' °^{H silox}y ^units (MeHSiO), T^H siloxy units (HS1O3/2). The organohydrogensiloxanes useful in the present invention may comprise any number of M,

M^H, D, D^H, T, T^H, or Q siloxy units, providing at least one siloxy unit contains SiH.

[0016] The organohydrogensiloxane may be selected from organopolysiloxane comprising siloxy units of the average formula:

(R2HS1O1 /2)(Si02)w(R2HSiOi /2)

(R₂HSi0₁/2)(Si0₂)w(R2SiO)x(R2HSi0₁/2)

(R₂HSiOi /2)(R2SiO)_x(R₂HSi0₁ /₂)

(R₃Si0₁/2)(R2SiO)_x(RHSiO)_y(R3Si0₁/2)

(R₃Si0₁/2)(R2SiO)_x(RHSiO)_y(RSi03/2)_z(R3Si0₁/2)

(R₃Si0₁/2)(R2SiO)_x(RHSiO)_y(Si02)w(R3SiOi/2)

where R is an organic group, alternatively R is a hydrocarbon group having 1 to 30 carbons, alternatively R is an alkyl group having 1 to 30 carbons, alternatively R is methyl, and w≥ 0, x≥ 0, y≥ 1 , and z is≥ 0.

[0017] In one embodiment of the present invention, the organohydrogensiloxane is selected from a dimethyl, methyl-hydrogen polysiloxane having the formula:

(CH3)3SiO[(CH3)2SiO]_x[(CH3)HSiO]ySi(CH3)3 0r (CH3)2HSiO[(CH3)2SiO]_xSiH(CH3)2 where x≥ 0, alternatively x = 1 to 500, alternatively x = 1 to 200, and y≥ 1 , alternatively y = 1 to 100, alternatively y = 1 to 50.

[0018] Methods for preparing organohydrogensiloxanes are well known, and many are sold commercially. Organohydrogensiloxanes are typically prepared by an acid catalyzed equilibration of a SiH containing siloxane with other siloxanes, such as cyclosiloxanes like octamethylcyclotetrasiloxane. The acid catalyst used in the equilibration reaction is "neutralized" upon completion of the equilibration reaction.

[0019] The organohydrogensiloxanes suitable in the present invention have an acid number of less than 0.005. The "acid number" is defined as the mass (in mg) of KOH needed to neutralized the acidic species per gram of the organohydrogensiloxane, as determined by titration techniques. The acid number of the organohydrogensiloxane may be determined by titrating the organohydrogensiloxane in an aqueous pyridine solution with a standardized NaOH solution of known normality. The end point may be determined by addition of an indicator, or alternatively, by potentiometric techniques. The acid number is determined by the following calculation:

(Volume of Titrant){Normality of r.tran ( g¾¾ (1000)

grams of ogranohydrogensiloxane

[0020] Such titration methods are well known in the art. One representative, non-limiting example is Dow Corning Corporation's Corporate Test Method - CTM 075 (Dow Corning Corp., Midland, Ml 48686).

[0021] Typically, an organohydrogensiloxane, suitable as component (B), is prepared in such a manner so the acid number is less than 0.005, or alternatively post treated after production, so as to ensure the acid number is reduced to less than 0.005. Such post treatments typically are effected by contacting the organohydrogensiloxane with a base, such as solid sodium bicarbonate, calcium carbonate, aqueous solutions of such bases, or a basic gas such as ammonia. The organohydrogensiloxane can be further contacted with other solid materials, such as ion exchange resins in a packed bed reactor, or solid carbon, to further reduce the acid number to even lower values. Typically, the organohydrogensiloxane is contacted with carbon, as described in US 60/683,754, which is herein incorporated by reference.

[0022] The organohydrogensiloxane useful as component (B) in the present invention has an acid number of less than 0.005, alternatively less than 0.003, or alternatively less than 0.0015.

[0023] In one embodiment of the present invention the organohydrogensiloxane has an acid number less than 0.0015 and the hydrosilylation reaction is done in a batch process.

[0024] Components (A) and (B) are reacted via a hydrosilylation reaction. Hydrosilylations are known in the art and require the addition of an appropriate hydrosilylation catalyst (C). Suitable hydrosilylation catalysts for use as component (C) in the present invention are known in the art and many are commercially available. Most commonly, the hydrosilylation catalyst is a platinum group metal and is added in an amount of 0.1 to 1000 ppm based on the weight of the reactants (A) and (B), alternatively 1 to 100 ppm of the platinum group metal. The hydrosilylation catalyst may comprise a platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium, or iridium metal or organometallic compound thereof, or a combination thereof. The hydrosilylation catalyst is exemplified by compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of said compounds with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or coreshell type structure. Complexes of platinum with low molecular weight organopolysiloxanes include 1 ,3-diethenyl-1 ,1 ,3,3- tetramethykdisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix.

[0025] Suitable hydrosilylation catalysts are described in, for example, U.S. Patents 3,159,601 ; 3,220,972; 3,296,291 ; 3,419,593; 3,516,946; 3,814730; 3,989,668; 4,784,879; 5,036,117; and 5,175,325 and EP 0347895 B1.

[0026] The hydrosilylation reaction can be conducted neat or in the presence of a solvent. The solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n- propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether; a halogenated hydrocarbon such as dichloromethane, 1,1 ,1-trichloroethane or methylene chloride, chloroform, dimethyl sulfoxide, dimethyl formamide, acetonitrile, Tetrahydrofuran, white spirits, mineral spirits, or naphtha.

[0027] The amount of solvent can be up to 50 weight percent, but is typically from 5 to 25 weight percent, said weight percent being based on the total weight of components in the hydrosilylation reaction. The solvent used during the hydrosilylation reaction can be subsequently removed from the resulting reaction product mixture by various known methods. Typically, this involves heating the contents of the reaction mixture under reduced pressure and collection the volatile solvent.

[0028] The amount of components (A) and (B) used in the hydrosilylation reaction can vary, and typically the amounts used are expressed as the molar ratio of the total unsaturated groups in component (A) vs the SiH content of component (B). Typically, the hydrosilylation reaction is conducted with a slight molar excess of the total unsaturated groups vs SiH to ensure complete consumption of the SiH in the hydrosilylation reaction. Typically, the hydrosilylation reaction is conducted with a 20%, alternatively 10%, alternatively 5%, or alternatively 1 % molar excess of the unsaturated group content of the polyether vs the molar SiH content of the organohydrogensiloxane.

[0029] In one embodiment, the hydrosilylation reaction is conducted such that greater than 99.5 mole % of the SiH of the organohydrogensiloxane reacts in the hydrosilylation reaction. The remaining SiH content may be determined by any analytical technique used in the art to measure SiH contents, such as Fourier Transform Infrared (FTIR) spectroscopy, and Si29 NMR techniques. Alternatively, the hydrosilylation reaction is conducted such that greater than 99.9 mole % of the SiH of the organohydrogensiloxane reacts in the hydrosilylation reaction. Alternatively, the hydrosilylation reaction is conducted such that no SiH content is detected by Si29 NMR techniques.

[0030] The hydrosilylation may be conducted in any batch, semi-continuous, or continuous process known in the art.

[0031] The inventive process disclosed herein can be used to prepare different types of silicone polyether structures, including "rake", ABA, and (AB)_n configurations.

EXAMPLES

[0032] These examples are intended to illustrate the invention to one of ordinary skill in the art and should not be interpreted as limiting the scope of the invention. All measurements were performed at 23 °C unless indicated otherwise.

[0033] The representative silicone polyethers prepared in the Examples utilized the following raw materials.

[0034] Allylpolyether - is a polyoxyethylene (-CH₂CH₂O-) polymer, terminated at one end with an allyl group and the other end with a OH, having an average Mw=800 g/mole by gel permeation chromatography using polystyrene standards for calibration. Average EO unit length of 11 by nuclear magnetic resonance spectroscopy. Alkali metal and alkaline earth metal content measured by inductively coupled plasma-mass spectrometry. The ICP-MS samples were diluted 50 fold in 2% HN03 and analyzed directly, with a detection limit of 0.100 parts per million. The Allylpolyether raw materials for all examples and comparison examples are described in Table 3.

[0035] Siloxane - refers to an organohydrogensiloxane of average structure M-D8.7DH3.7- M produced by acid catalyzed equilibration of M, D, and DH siloxane intermediates. The "acid number" of the organohydrogensiloxane was determined by Corporate Test Method #0756 (Dow Corning Corporation, Midland Mich.). All of the following examples use a siloxane with acid number of <0.001 mg KOH/g acid equivalent.

[0036] The representative silicone polyethers prepared in these Examples utilized the following process.

[0037] Process 1 : Loaded 710.0 grams of Allylpolyether and 290.0 grams Siloxane into a 2 L reaction calorimeter (Mettler-Toledo RC-1). No additional alkali or alkaline earth metals were added during the hydrosilylation Process 1 beyond those from the Allylpolyether. Heated reactor contents to 80 °C in isothermal mode, under a nitrogen atmosphere and with an agitation rate of 600 rpm. Added 0.20 ml of a solution which contains a platinum hydrosilylation catalyst diluted to 2 wt % Pt in isopropanol (3.1 μg Pt per g reactants). Upon addition of catalyst, an exothermic reaction was initiated. The calorimeter is capable of controlling temperature within +/-1 °C of isothermal while continuously measuring the thermal energy being released by the exothermic chemical reaction. The rate of heat evolution is proportional to rate of the reaction and is plotted either as Kilojoules vs time or as percent Conversion vs time. When the exotherm was observed to have finished (reactor temperature and reactor jacket temperature returned to their values prior to catalyst addition and were no longer changing), the reactor contents were maintained at temperature for an additional 10 minutes, then cooled to less than 50° Celsius before being exposed to air. The total conversion achieved in the reaction can be expressed as the total enthalpy evolved during the reaction time. The Total Enthalpy specification for complete reaction is at least 135 kiloJoules. A sample may be taken to test for residual silicon hydride content using Corporate Test Method #0806-1014A (Dow Corning Corporation, Midland Mich.)

[0038] Example 1

A silicone polyether was prepared using Process 1 with an Allylpolyether containing 0.924 parts per million residual Na, 0.433 parts per million residual K, and no detectable residual Mg or Ca and siloxane with <0.001 mg KOH/g acid equivalent (acid number). The reaction had a total enthalpy of 135.0 kiloJoules. A value of at least 135 kiloJoules is acceptable because it corresponds to a sufficiently complete reaction.

[0039] Example 2

A silicone polyether was prepared using Process 1 with an Allylpolyether containing 0.558 parts per million residual Na, 0.446 parts per million residual K, and no detectable residual Mg or Ca and siloxane with <0.001 mg KOH/g acid equivalent (acid number). The reaction had a total enthalpy of 136.1 kiloJoules.

[0040] Comparison Example 1

A silicone polyether was prepared using Process 1 with an Allylpolyether containing 0.743 parts per million residual Na, 1.769 parts per million residual K, 1.047 parts per million residual Mg, and 0.125 parts per million residual Ca, and siloxane with <0.001 mg KOH/g acid equivalent (acid number). The reaction had a total enthalpy of 131.6 kiloJoules.

[0041] Comparison Example 2

A silicone polyether was prepared using Process 1 with an Allylpolyether containing 2.661 parts per million residual Na, 0.593 parts per million residual K, 0.326 parts per million residual Mg, and 0.102 parts per million residual Ca, and siloxane with <0.001 mg KOH/g acid equivalent (acid number). The reaction had a total enthalpy of 123.7 kiloJoules.

[0042] Comparison Example 3

A silicone polyether was prepared using Process 1 with an Allylpolyether containing 10.34 parts per million residual Na, 0.113 parts per million residual K, 0.759 parts per million residual Mg, and no detectable residual Ca. The reaction had a total enthalpy of 112.8 kiloJoules.

[0043] Comparison Example 4

A silicone polyether was prepared using Process 1 with an Allylpolyether containing 37.2 parts per million residual Na, 0.102 parts per million residual K, and no detectable Mg or Ca, and siloxane with <0.001 mg KOH/g acid equivalent (acid number). The reaction had a total enthalpy of 131.7 kiloJoules.

[0043] f f p 0 O M p

[0044]

[0045]

Claims

What is Claimed is:

1. A process for preparing a silicone polyether comprising reacting a mixture comprising:

(A) a polyether having at least one terminally unsaturated aliphatic hydrocarbon group and an alkali metal content of less than 10 ppm and an alkaline earth metal content less than 0.4 ppm;

(B) an organohydrogensiloxane having an acid number of less than 0.005; and

(C) a hydrosilylation reaction catalyst

wherein greater than 99.5 mole % of the SiH of the organohydrogensiloxane reacts in the hydrosilylation reaction.

2. The process of claim 1 wherein the polyether (A) has the average formula

R 0(CnH_2nO)_mR²

where n is from 2 to 4 inclusive,

m is greater than 2,

R¹ is an unsaturated aliphatic hydrocarbon,

R² is R¹ , hydrogen, an acetyl group, or a monovalent hydrocarbon containing 1 to 8 carbons.

3. The process of claim 2 where n =2, R¹ is an allyl group, and R² is hydrogen.

4. The process of Claim 1 wherein (A) is

H₂C=CHCH₂0(C2H₄0)_aH,

H₂C=CHCH₂0(C2H40)_aCH_3i

H₂C=CHCH₂0(C2H40)_aC(0)CH_3i

H₂C=CHCH₂0(C2H40)_a(C₃H₆0)_bH,

H₂C=CHCH₂0(C2H40)_a(C3H₆0)_bCH_3i

H₂C=C(CH₃)CH₂0(C₂H₄0)_aH,

H₂C=CC(CH₃)₂0(C₂H₄0)_aH,

H₂C=C(CH₃)CH₂0(C₂H₄0)_aCH_3i

H₂C=C(CH₃)CH₂0(C₂H₄0)_aC(0)CH_3i

H₂C=C(CH₃)CH₂0(C₂H₄0)_a(C₃H₆0)_bH,

H₂C=C(CH₃)CH₂0(C₂H₄0)_a(C₃H₆0)_bCH_3i

HC≡CCH₂0(C₂H₄0)_aH, HC≡CCH₂0(C2H40)_aCH_3i

HC≡CCH₂0(C2H40)_aC(0)CH_3i

HC≡CCH₂0(C2H40)_a(C3H₆0)_bH, or

HC≡CCH₂0(C2H40)_a(C₃H₆0)_bCH3

wherein a and b are greater than 0, alternatively a and b independently may range from 0 to 40, with the proviso that a + b > 2.

5. The process of claim 1 wherein (B) is selected from an organopolysiloxane having the average formula:

(R₂HSi0₁/2)(Si02)_w(R2HSi0₁/2),

(R₂HSi0₁/2)(Si0₂)w(R2SiO)x(R2HSi0₁/2),

(R₂HSiOi _/2)(R2SiO)x(R2HSi0₁ /₂),

(R₃Si0₁/2)(R2SiO)_x(RHSiO)_y(R3Si0₁/2),

(R₃Si0₁/2)(R2SiO)_x(RHSiO)y(RSi03/2)_z(R3Si0₁/2), or

(R₃Si0₁/2)(R2SiO)_x(RHSiO)_y(Si02)w(R3SiOi/2)

wherein R is an organic group, w≥0, x≥0, y≥1 , and z is≥0.

6. The process of claim 5 wherein the organohydrogensiloxane is a dimethyl, methyl- hydrogen polysiloxane having the formula

(CH₃)₃SiO[(CH₃)₂SiO]_x[(CH₃)HSiO]ySi(CH₃)₃ or

(CH₃)₂HSiO[(CH₃)₂SiO]_xSiH(CH₃)₂

where x≥0 and y≥2.

7. The process of claim 1 wherein (C) is a platinum group metal.

8. The process of Claim 7 wherein the platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium, or iridium metal or organometallic compound thereof, or a combination thereof.

9. The process of Claim 1 , wherein (C) is a platinum compound selected from chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, complexes of chloroplatinic acid, chloroplatinic acid hexahydrate, and platinum dichloride with low molecular weight organopolysiloxanes, platinum compounds microencapsulated in a resin matrix orcoreshell structure.

10. The process of claim 1 where the molar ratio of the unsaturated groups of the polyether A) to the SiH content of the organohydrogensiloxane B) is greater than one.

11. The process of claim 10 wherein the polyether A) has the formula

H₂C=CHCH₂0(C2H₄0)_aH

where a is greater than 2,

and organohydrosiloxane B) has the average formula

(CH3)3SiO[(CH3)2SiO]_x[(CH3)HSiO]ySi(CH3)3

where x≥0 and y≥1.

12. The process of claim 1 wherein greater than 99.9 mole % of the SiH of the

organohydrogensiloxane reacts in the hydrosilylation reaction.

13. The process of claim 1 wherein the mixture further comprises (D) a solvent.

14. The process of claim 13 wherein (D) is selected from an alcohol, a ketone, an aromatic hydrocarbon, a glycol ether, a halogenated hydrocarbon, chloroform, dimethyl sulfoxide, dimethyl formamide, acetonitrile, tetrahydrofuran, white spirits, mineral spirits, or naphtha.

15. The process according to claim 1 wherein the hydrosilylation reaction occurs in a continuous process.

16. The process according to claim 14 wherein the continuous process occurs in a plug flow reactor.